Naphthoquinone imine compositions and method for using the same



United States Patent Office 3,516,778 NAPHTHOQUINONE IMINE COMPOSITIONSAND METHOD FOR USING THE SAME Walter H. Brunner, Easton, Pa., assignorto Clairol Incorporated, New York, N.Y., a corporation of Delaware NoDrawing. Continuation-impart of application Ser. No.

345,107, Feb. 17, 1964. This application June 9, 1964, Ser. No. 373,838

Int. Cl. A61k 7/12 US. Cl. 8-1.0.2 16 Claims ABSTRACT OF THE DISCLOSUREA method and a composition for dyeing living human hair on the headwhich involves a composition containing a tinctorial amount of a hairsubstantive naphthoquinone imine.

This application is a continuation-in-part of application Ser. No.345,107, filed Feb. 17, 1964, now abandoned.

This invention relates to a method of dyeing hair and, moreparticularly, to a method for dyeing living human hair on the head. Italso concerns novel hair dyeing compositions which are useful for thispurpose and certain novel compounds that can be employed in formulatingthese compositions.

There are relatively few dyes which are known to be suitable for dyeingliving human hair on the head by direct dyeing methods and which givestrong permanent coloration to the hair at temperatures which arecomfortably tolerated by the body, e.g., temperatures of less than about40 C. Most hair dyes require various peroxides for the development ofcolor, or the use of various dyeing assistants, some of which irritateor cause staining of the skin.

The direct dyes which have been proposed for dyeing human hair eithergive only surface coloration to the hair without suflicient penetrationof the dye into the hair shaft, and thus rinse off or rub off easily, orthey stain the scalp, or require various assistants in obtaining gooddyeing. By direct dye is meant herein a dye which will penetrate intothe hair shaft and give coloration to the hair without subsequent orsimultaneous additional manipulations, such as reaction with peroxides.

The nitrophenylenediamine derivatives, which have been used for directdyeing of the hair, generally give only weak dyeings which wash outreadily and produce relatively light colors, such as yellows, reds, andat their deepest, violets. Hence, they are not satisfactory for makingdrab mixtures, nor dark browns nor blacks.

It has now been found that certain naphthoquinone imines can be used todye human hair at temperatures which are below 40 C. It is not necessaryto apply these derivatives as thick viscous pastes, and highconcentrations of dye, surfactants, or solvents and other dyeingassistants are not necessary for obtaining proper dyeing of the hair.Furthermore, the naphthoquinone imine compositions of this invention donot stain or irritate the scalp or damage the hair.

The dyes utilized in this invention are direct dyes which show asurprisingly high affinity for hair under aceptalble conditions ofapplication. They, therefore, give strong shades of a generallypermanent nature. In general, they work over a wide range of pH and bathcomposition and give essentially uniform strengths on the various kindsof human hair, such as natural gray, permanent-waved 3,516,778 PatentedJune 23, 1970 this reason they are suitable as a base for drab mixtures,and particularly, for dark browns and blacks.

The dyes employed in this invention have the further advantages over theknown dyes in that they are, in general, stable on storage. This lastadvantage is of importance, since hair dyes are commonly marketed asaqueous compositions at pHs varying from about 3 to 10. Under storageconditions for long periods (say one year), and particularly in warmclimates, the large majority of existing dyes undergo deterioration andshow lower dye strength or a shade change when applied to hair.

The naphthoquinone imines that may be employed in accordance with thepresent invention are hair substantive naphthoquinone imines that arepreferably water-soluble or water-dispersible and described by theformula:

and tautomeric forms thereof, wherein:

(1) X is selected from the group consisting of the monovalent radical Rand the divalent radical --R'-; wherein R may be hydrogen, monovalentaliphatic, monovalent cycloaliphatic, monovalent aryl, monovalentaralkyl and monovalent heterocyclic radicals and wherein R'-may bedivalent aliphatic, divalent cycloaliphatic, divalent arylene, divalentaralkyl and divalent heterocyclic radicals.

(2) r is the number 1 or 2; r being 1 when X is monovalent, and r being2 when X is divalent.

(3) A, B, C, D, E and G are selected from the group consisting ofhydrogen, chlorine, bromine, sulfo, alkyl and the radical HNR, in which-R has the value ascribed to it above and wherein A and/or B may also behydroxy.

In a more particular form of the invention, the naphthoquinone iminesthat may be employed are hair substantive naphthoquinone imines that arepreferably watersoluble or water-dispersi-ble and described by theformula:

OH 1 q X and tautomeric forms thereof, in which:

(1) X and r have the same values ascribed to them above in connectionwith Formula I;

(2) A is selected from the group consisting of hydroxy and the radicalHNR in which R has the value ascribed to it above; and

(3) C, D, E and G are selected from the group consisting of hydrogen,chlorine, bromine, sulfo and alkyl.

In a preferred form of this invention C, D, E and G in Formula II ishydrogen.

As noted above, the radical X in Formulas I and II above may be amonovalent radical -R or a divalent radical 4R'-. When reference is madeherein to the monovalent character of the radical X, the term 'R will beemployed. On the other hand, the term R-' will be used to designate thedivalent aspects of radical X.

When R in Formulas I or II above is a monovalent aliphatic radical, itmay take various forms. Thus, for example, it may be an alkyl,monohydroxyalkyl, polyhydroxyalkyl, -(alkylene-NH) 1-alky1ene-OH,wherein n is a whole number from 1 to 3; {alkylene-NHL, alkylene- NHwherein n is a whole number from 1 to 3, etc.

When --R in Formulas I or 11 above is alkyl, it may be a straight chainor branched chain alkyl radical which is preferably lower alkyl, e.g.,having from 1 to 6 carbon atoms. By way of illustration the followingalkyl groups may be mentioned as typical examples: methyl, ethyl, npropyl, isopropyl, n-butyl, sec. butyl, tert. butyl, n-amyl, isoamyl,n-hexyl, and the like.

In the case where R is a hydroxyalkyl radical in Formulas I and II, itmay be a monohydroxyor polyhydroxyalkyl radical. The alkyl chain ispreferably a lower alkyl chain having from 2 to 6 carbon atoms. Typicalmono and polyhydroxyalkyl radicals of this character are Z-hydroxyethyl;3-hydroxypropyl; 2-l1ydroxypropyl; tris- (hydroxymethyl)methyl; 1,3dihydroxy-Z-methyl-propyl; 2,3-dihydroxypropyl; 1,3-dihydroxy-2-propyl,etc.

When R in the Formulas I or II has the value -(alkylene-NH--)-alkylene-NH or -(alkyleneNH) 1-a1kylene-OH, the alkylene radicals areusually the same lower alkylene radicals which may be straight chainedor branched, and ordinarily do not exceed 3 or 4 carbon atoms. In thiscase n or n is a number that ranges from 1 to 3. Typical alkyleneradicals are the trimethylene radical (-CH CH -CH the ethylene radical 22) the tetramethylene radical (CH (CH --CH the propylene radical -CHCHZthe isobutylene radical cu b-H?- etc.

When the compounds of this invention take the form shown in Formula I orII, where X is the divalent radical R, this divalent radical bridges twohalves of the molecule, which are identical. -R'- may be a divalentalkylene, straight chained or branched, in which event it preferably isa lower alkylene radical having, e.g., from 2 to 6 carbon atoms. Typicalexamples are ethylene, trimethylene, tetramethylene, propylene,isobutylene, pentamethylene, etc.

In another case the divalent radical R'- may be a hydroxyalkyleneradical. In the preferred examples of this type this radical will havefrom 3 to 6 carbon atoms, such as Z-hydrOxytrimethylene;2-hydroxytetramethylene; 2,3-dihydroxytetramethylene; andhydroxyisobutylene.

-R- may be constituted as the radical -(alkylene NH) -a1kylene-, inwhich u may have a value which is 1, 2 or 3, and the alkylene moiety isa lower alkylene radical, e.g., having 1 to 6 carbon atoms. Typicalradicals of this character are as follows: 2,2'-iminodiethyl, i.e., -CHCH NHCH -CH 3,3-iminodipropyl, i.e., 2,2'-iminodipropyl, i.e.,

The radical -R may also be an aryl radical and preferably, a mono or abicyclic aryl radical having up to 12 carbon atoms in the ring system.These will ordinarily take the form of substituted or unsubstitutedphenyl, naphyl or biphenylyl radicals. The substituted radicals maycontain any of a variety of substituents or combinations thereof. By wayof example the following may be mentioned: alkyl, alkenyl, hydroxy,alkoxy, nitro, halogen, amino, alkylamino, dialkylamino,hydroxyalkylamino, bishydroxyalkylamino, acylamido, monohydroxyalkyl,polyhydroxyalkyl, carbalkoxy, carbamoyl, N-alkylcarbamoyl,N,N-dialkylcarbamoyl, cyano, sulfamoyl, N-alkylsulfamoyl,N,N-dialkylsulfamoyl, alkanoyl, mercapto, alkylthio, and alkylsulfonyl.In this case the alkyl moieties are also preferably lower alkyl.Moreover, the halogen may be chlorine, bromine, fluorine or iodine.Typical examples include phenyl; 0-, m-, p-tolyl; 4-ethylpheny1;2,4-xylyl; 4- alkylphenyl; 4 isopropenylphenyl; 2 ethoxyphenyl; 4-ethoxyphenyl; Z-methoxyphenyl; 3-methoxyphenyl; 4-methoxyphenyl;4-hydroxyphenyl; Z-hydroxyphenyl; 3-hydroxyphenyl; I i-nitrophenyl;2-chlorophenyl; 2-fluorophenyl; 3-bromophenyl; 4-iodophenyl;3-aminophenyl; 4-methylaminophenyl; 4 diethylaminophenyl;dimethylaminophenyl; 4bis(hydroxyethyl)aminophenyl; 3 acetamidophenyl;4-acrylamidophenyl; 4-benzamidophenyl; 3-glycolylamidophenyl;3-hydroxymethylphenyl; 4-(2-hydroxyethyl)phenyl; 4 (2,3dihydroxypropyl)phenyl; 3 carbethoxyphenyl; 4 carbamoylphenyl;3-(N-methylcarbam- 0yl)phenyl; 2-cyanophenyl; 3-cyanophenyl;4-sulfamoylphenyl; 4-(N,N-bishydroxyethylsulfamoyl)phenyl;3-acetylphenyl; 3-propionylphenyl; 4-methy1mercaptophenyl; 3-methylsulfonylphenyl; 3-nitro-4-aminophenyl; 2-methyl-5- nitrophenyl; 3nitro-4-hydroxyphenyl; 2-chloro-5-nitro phenyl;4-chloro-3-methoxyphenyl; 4-acetamido-2-methy1- phenyl;4-acetamido-3-methoxyphenyl; 2 carbamoyl-4- chlorophenyl;2-methyl-S-sulfamoylphenyl; 2-chloro-5-cyanophenyl; 2hydroxy-5-sulfamoylphenyl; 3-nitro-4-hydroxyethylaminophenyl; 3-nitro 4methylaminophenyl; 3-chloro 5 nitrophenyl; Z-hydroxy-S-nitrophenyl;2-methoxy-S-nitrophenyl; 3 nitro 4 dirnethylaminophenyl; 2-hydroxy 3chloro-S-sulfamoylphenyl; 7-hydroxy-2- naphthyl; 4-hydroxy-2-naphthyl;6-sulfamoyl-2-naphthyl; 1 methoxy-6-sulfamoyl-Z-naphthyl; 4 biphenylyl;2-biphenylyl; 4-acetamido-4-biphenylyl.

When X is a mono or bicyclic aryl radical in Formulas I and B, itpreferably is a substituted radical of this character. It has been foundthat certain substituted aryl radicals, as hereinafter described, have agreater substantivity for hair than the unsubstituted aryl radicals.

When R is an aralkyl radical in Formulas I or II above, it will besimilar in general character to the aryl radical described above. Itwill, however, be bonded to the irnino nitrogen of the naphthoquinoneimine nucleus through its alkyl moiety. Examples of aralkyl radicals forthe purpose are benzyl, p-chlorobenzyl; 3-methoxybenzyl; 2,4-dihydroxybenzyl; Z-phenylethyl; 1-phenylethyl; l-phenylpropyl;Z-phenylpropyl; 2-naphthylmethyl, and the like.

When 'R is a cycloaliphatic radical, it may have up to 6 carbon atoms inthe ring structure, the cyclohexyl or cyclolpentyl being preferred. Itmay, in general, also carry the various substituents described above inconnection 'with the substituted aryl radicals. As examples of suitablecycloaliphatic radicals, there may be mentioned: cyclopentyl;cyclohexyl; Z-hydroxycyclohexyl; 2-oxo-cyclohexyl; 3-methylcyclohexyl;4-methylcyclohexyl; 3-chlorocyclohexyl; 4-methoxycyclohexyl, and thelike.

When R'- is a divalent arylene radical, it is preferably monocyclic orbicyclic in character, e.g., m-phenylene, p-phenylene, p-toluylene;4,4'-biphenylene; 3,3- tlimethyl-4,4-biphenylene;3,3'-dichloro-4,4'-biphenylene, and the like. Substituted andunsubstituted arylene radicals are suitable, although generally theunsubstituted radical will be utilized.

Similarly when R- is a divalent cycloaliphatic radical, it preferablycontains up to 6 carbon atoms, the preferred radical being the divalent1,2-; 1,3-; or 1,4- cyclohexylene radical. When R is a divalent aralkylradical the two valence bonds of the radical may both issue from thesame alkyl moiety, as for example in the aralkyl radicals phenylethyleneand Z-phenyltrimethylene (IEI2C-CHCH2) or from different alkyl moieties,as in mor p-phenylenedimethylene (H CC H -CH or one bond may issue froman alkyl moiety and the other from an aryl moiety, as in mor-p-phenylenemethylene When X is a heterocyclic radical in Formulas I orII above, it may take the form of the monovalent radical R or divalentradicals R or RR' in which each of R or R is a heterocyclic ringstructure containing up to and including three rings and 14 atoms insaid ring structure. The heteroatoms of these ring structures may beselected from the group consisting of O, S, N or combinations thereof,and preferably each ring structure represented by R or R'- contains nomore than 3 heteroatoms. When the divalent heterocyclic radical has theform R'R-, the Rs may be bonded to each other through a disulfidelinkage, such as In the case of the heterocyclic radicals, thesubstituents on the ring or rings of these radicals can varyconsiderably. These include one or more alkyl, hydroxy, nitro, halogen,amino, alkylamino, hydroxyalkylamino, alkoxy, monohydroxyalkyl,polyhydroxyalkyl, dialkylamino, bishydroxyalkylamino, cyano, carbamoyl,sulfamoyl, etc., or combinations thereof. In this case also the alkylradical, and the alkyl moiety of the substituted alkyl raldical are ofthe lower alkyl type. The halogen can be chlorine, bromine, fluorine oriodine. Typical examples of the heterocyclic radicals are Z-pyridyl,3-pyridyl, 4-pyridyl, 6-amino-2-pyridyl, 2-methyl-4-thiazolyl,4-quinolyl, quinolyl, 7-quinolyl, 2-imidazolyl, S-benzimidazolyl, 2-benzothiazolyl, 2-mercapto-5benzothiazolyl, Z-naphtho- [1,2 thiazolyl,-etc.

When C, D', E, G and X of Formula II above are hydrogen, A is amino andr is 1, the compound is one which is well-known in the prior art asnaphthazarin intermediate, hereinafter referred to as NI. This compoundand compounds of like character exist in at least two tautomeric formswhich may be expressed by the following equation:

These are included in the present invention.

Embraced within the present invention are the naphthoquinone imines ofthe formula:

III 0 H III-R I ll OH O and tautomeric forms thereof wherein R has thevalue ascribed to it above. In a preferred form of these compounds, theradical R is an aminoalkylaminoalkyl radical of the formula -alkyleneN-nH H wherein alkylene is a lower alkylene radical and n is a number of 1to 3. These are a novel group of compounds and are prepared by thecondensation of an alkylenepolyamjne-eg,

wherein rr=1 to 3--and preferably a polyalkylenepolyamine of the formulawith naphthazarin, i.e., 5,8-dihydroxy-1,4-naphthoquinone. Thecondensation is preferably carried out in an aqueous medium utilizing alarge excess of the amine (e.g., 4 to 6 moles). The time of thecondensation may vary between five minutes to several hours. However,best results are obtained in about 5 to 10 minutes. Similarly, thetemperature may vary considerably between 40 to 100 C., but the optimumtemperature is about 100 C.

The NI derivative which may be utilized in accordance 'with the presentinvention may be described by the general formula:

and tautorneric forms thereof wherein C, D', E, G, X, and r have thesame value ascribed them in connection with Formula II. In those caseswhere X is a monovalent or divalent radical other than hydrogen, thesecompounds are prepared by condensing NI with a primary amine or diamine,preferably in the presence of an excess of the amine. The excessof amine*will vary from a slight excess to 'a six-fold excess depending on theparticular primary amine employed.

The reaction temperature and time will also vary with the particularreactants that are employed and the solvent system utilized. In general,however, the reaction will go at temperatures up to the refluxtemperature of the reaction medium which will generally be in theneighborhood of about C. to C. Similarly, the reaction time may varyfrom 10 to 15 minutes up to about eight hours.

The solvent systems that can be employed will depend on the particularagents that are being condensed. These may be aqueous systems, as wellasorganic solvent systems. Particular solvents that have been employedinclude water, ethanol, isopropanol and glacial acetic acid.

With regard to NI reaction products generally illustrated in Formula IVabove, it has been found that several classes of these compounds, whichare noval, have particularly desirable properties as dyes for hair. Onegroup of compounds of special interest are defined by the formula:

and tautomeric forms thereof wherein R" is a hydroxyalkyl radical of 2to 6 carbon atoms which may be monohydroxyalkyl or polyhydroxyalkyl or ahydroxyalkylaminoalkyl radical. Such derivatives are generallycharacterized not only by a high degree of dispersibility in aqueousmedium, but also by a surprisingly high aflinity to various types ofhair, particularly to bleached hair, as compared with the correspondingderivatives in which R is merely an alkyl group (e.g., ethyl). Asexamples of R which are in this novel and favorable class, there may bementioned Z-hydroxyethyl; 3-hydroxypropyl; 2- hydroxypropyl;2,3-dihydroxypropyl; tris(hydroxymethyl) methyl;1,3-dihydroxy-2-methylpropyl; 1,3 dihydroxy-Z- propyl, as well as2(2-hydroxyethylamino)ethyl; 3(2-hydroxyethylamino)propyl; 1(2hydroxyethylamino) 2- propyl; 1(Z-hydroxyethylamino)2-methyl-2-p-ropyl;etc.

Another useful and novel class of NI derivatives are described by theformula:

and tautomeric forms thereof in which R and R are selected from thegroup consisting of H, monohydroxyalkyl and polyhydroxyalkyl, at mostone of R and R being hydrogen; and R is selected from the groupconsisting of H and the radical in which R and R have the same valueascribed to them above.

A typical group of compounds falling within Formula VI above is'thatwherein only R and R are hydrogen. Also of interest are compoundswherein R is hydrogen, whereas R and R or both are hydroxyethyl;2,3-dihydroxypropyl and the like. The case wherein both nitrogens carryorganic substituents such as:

VII

1] HO onrmnQ-rm VIII OH H ll NH2 O NH;

or tautomeric forms thereof wherein -R' has the same value ascribed toit in connection with Formula II. Of particular interest and novelty arethe compounds prepared from the aliphatic diamines, i.e., aliphaticcompounds containing at least two primary amino groups. Typical examplesof the alkylene radical -R' which are suitable for this class areethylene, trimethylene, tetramethylene, propylene, isobutylene,pentamethylene, etc. Also suitable for this class of dyes are thosecontaining the diradical -(alkylene NH) s-alkylene-, such as 2,2-iminodiethyl; 2,2-iminodipropyl;

and the like. These are prepared from the correspondingpolyalkylenepolyamines, such as diethylenetriamine;triethylenetetramine; 2,2'-iminodipropylamine; 3,3'-iminodipropylamine;bis-hexarnethylenetriarnine and the like.

The reaction of NI with amino-substituted heterocyclic compounds producea class of compound which is also worthy of special mention. Moreparticularly, these can be defined by the formula: 1X 1 NQL H,

NHz ll 0 or tautomeric forms thereof in which R is a monovalent ordivalent heterocyclic radical and r is 1 or 2, r being 1 when R is amonovalent radical, and r being 2 when R" is a divalent radical. By wayof example R may be Z-pyridyl, 3-pyridyl, 4-pyridyl, -6-amino-2-pyridyl, 2-methyl-4-thiazolyl; 4-quinolyl, S-quinolyl, 7- quinolyl,2-imidazolyl, S-benzimidazolyl, 2-benzothiazolyl, 2-naphtho 1,2]thiazolyl.

When the heterocyclic reactant contains two reactive amino groups, thecompound produced may contain a divalent heterocyclic moiety, in whicheach valence of said moiety is bonded to a NI nucleus through nitrogen.This might also result from the use of a heterocyclic amine whichcontains one amino group and one functional group capable of reactingwith a functional group of another molecule of the same material toproduce in effect a heterocyclic amine containing two amino groups. Byway of illustrating the latter, the reaction of NI withS-amino-2-mercaptobenzimidazole may give a compound having the followingstructure:

OHN I II The naphthoquinone imines utilized in the present invention canbe employed to prepare basic or acidic dye compositions and because oftheir stability, may be used in conjunction with oxidation dyes.Furthermore, they may likewise be included in hair dyeing compositionswhich contain other direct dyeing dyes that also may or may not containan oxidation dye. A variety of direct dyeing dyes are known in the priorart which are useful for this purpose. They include nitro dyes, azodyes, anthraquinone dyes, etc. By way of illustration, any of the nitrodyes disclosed in the following US. patents may be used in conjunctionwith the naphthoquinone imines: 2,750,326; 2,750,327; 3,088,877;3,088,878 and 3,08,978.

The pH of the dye compositions of this invention can vary from about 2.5to 11. In the acid range the pH of about 3.5 to 6 is suitable. It ispreferred, however, that the compositions be in the alkaline range andparticularly at a pH of about 7.5 to 10. Any selected water-dispersablecompatible alkalizing agent (if it is desired to have the compositionsin the alkaline range) can be used to give the desired pH. The quantityof the alkalizing agent employed can vary over a wide range depending onthe dye and particular alkalizing agent employed and the desired pI-I.Illustratively, the 'alkalizing agent can vary from less than about 0.1%to about 10% and preferably, from about 0.25% to about by weight of thecomposition.

The alkalizing agent is selected so that it will not interfere (i.e., iscompatible) with the dye employed, and will not precipitate the dye orintroduce any possibility of toxicity under the conditions of use, orinjure the scalp at its ultimate concentration in the composition to beapplied to the keratinaceous material. A primary test of some selectedalkalizing agent can be made to note its compatibility with the dye orto discover possibility of toxicity or injury.

Ammonium hydroxide because of its freedom from toxicity over a wideconcentration range and its economy, is an acceptable alkalizing agent.However, there can be used in place of, or together with, ammonia anyother compatible ammonia derivative as an alkalizing agent, such as analkylamine, such as ethylamine, dipropylamine, or triethylamine, analkanediamine, such as 1,3- diaminopropane, an alkanolamine, such asethanolaminc or diethanolamine, a polyalkylenepolyamine, such asdiethylenetriamine, or a heterocyclic amine, such as morpholine.

Also, as alkalizing agent, any alkaline earth hydroxide, for example,calcium hydroxide or magnesium hydroxide, can be used up to the limit ofits water solubility and at any concentration that fails to produce aprecipitate with any of the components of the composition. The dissolvedalkaline earth hydroxides are preferred over the alkali metalhydroxides, such as sodium hydroxide, or potassium hydroxide, orcarbonates, such as sodium carbonate and bicarbonate, any of which canalso be used so long as their ultimate concentration in the final dyeingsolution is below that which might possibly irritate the scalp.

The alkalizing component of choice, however, is a water-soluble organicamine of low volatility (3.1. higher than about 50 C.) having less thanabout 12 carbon atoms, such as n-propylamine, isobutylamine,Z-ethylbutylamine, diethylamine, triethylamine. Particularly suited asthe alkalizing agent are the following: (A) primary aliphatic diamines,such as ethylenediamine; 1,2- diaminopropane; 1,3-diaminopropane;diethylenetriamine; triethylenetetramine; 2,2-iminodipropylamine;3,3-iminodipropylamine; and bis-hexamethylenetriamine; (B)alkanolamines, such as ethanolamine; isopropanolamine; diethanolamine;di-isopropanolamine; triethanolamine; triisopropanolamine;N-methyldiethanolamine; diisopropylethanolamine;dimethylisopropanolamine; 2-amino-2- methylpropane-l, 3-di0l; tris(hydroxymethyl methylamine and the like, which may also have a phenylsubstituent, e.g., N-(Z-hydroxyethyl)aniline;N-methyl-N-(2-hydroxyethyl)aniline; N,N-bis(2-hydroxyethyl)aniline; and(C) heterocyclic amines, such as morpholine, N-methylmorpholine,N-ethylmorpholine, N-hydroxyethylmorpholine, N-phenylmorpholine,piperidine, N-hydroxyethylpiperi dine, and piperazine.

The pH of the composition may be adjusted with any inorganic or organicacid or acid salt which is compatible with the composition and will notintroduce toxicity under its conditions of use, especally when acidcompositions are desired. Illustrative of acids or acid salts there canbe mentioned: sulfuric, formic, acetic, lactic, citric or tartaric acid,or ammonium sulfate, sodium dihydrogen phosphate, or potassiumbisulfate.

Water-soluble surface active agents can also be employed in the dyeingcompositions utilized in this invention. These can be anionic, non-ionicor cationic. Illustrative of the various types of water-soluble surfaceactive agents there can be mentioned: higher alkylbenzenesulfonates;alkylnaphthalenesulfonatess; sulfonated esters of alcohols and polybasicacids; taurates; fatty alcohol sul- 5 fates; sulfates of branched chainor secondary alcohols; alkyl dimethylbenzyl ammonium chlorides; and thelike. Illustrative of specific surfactants there can be mentioned:lauryl sulfate; polyoxyethylene lauryl ester, myristyl sulfate; glycerylmonostearate; sodium salt of palmitic methyl taurine; cetyl pyridiniumchloride; lauryl sulfonate; myristyl sulfonate; lauric diethanolamide;polyoxyethylene stearate; stearyl dimethyl benzyl ammonium chloride;dodecyl benzene sodium sulfonate; nonyl naphthalene sodium sulfonate;dioctyl sodium sulfosuccinate; sodium N-methyl-N-oleoyl taurate; oleicacid ester of sodium isothionate; sodium dodecyl sulfate; the sodiumsalt of 3,9-diethyl tridecanol-6-sulfate and the like. The quantity ofwater-soluble surface active agent can vary over a wide range, such asthat of from about 0.25% to and preferably from about 0.25% to 10% byweight of the composition.

A thickening agent can also be incorporated in the present dyeingcomposition which may be one or several of those commonly used in hairdyeing, such as sodium alginate or gum arabic, or cellulose derivatives,such as methylcellulose, or the sodium salt of carboxymethylcel lulose,or acrylic polymers, such as polyacrylic acid sodium salt, or inorganicthickeners, such as bentonite. The quantity of thickening agent can varyover a wide range, such as that of from about 0.1% to and preferablyfrom about 0.5% to 5% by weight.

Tinctorially effective quantities of the naphthoquinone imines in thecompositions of this invention can vary over a wide range, such as thatof about 0.01% to greater than about 5%, e.g., 10%, by weight of thecomposition, and preferably from about 0.01% to about 2% by weight. Thewater content of the composition is ordinarily the major constituent andcan vary over a wide range dependent in large measure on the quantity ofother additives. Thus, the water content can be as little as 10%, andpreferably from about 70% to 99%.

The dyeing compositions of this invention are preferably aqueouscompositions. The term aqueous composition is used herein in its usualgeneric sense as embracing any water-containing composition embodied inthe invention. This includes true solutions of the dye in an aqueousmedium, either alone or in conjunction with other materials, which arealso dissolved or dispersed in the aqueous medium. The term aqueouscomposition also encompasses any mixture of dye with the aqueous mediumeither alone, or together with other ingredients. The dye may becolloidally dispersed in the medium or may merely be intimately mixedtherein.

The term aqueous medium as used herein, includes any medium whichcontains Water. Thus, the aqueous medium may be an aqueous alkaline oraqueous acid medium. Moreover, the aqueous medium may comprise water anda solvent, e.g., ethanol. The latter may be employed as a common solventto enhance the solution of the dye or some other organic material.

The aqueous compositions of this invention may take many forms. Thus,they may be thin or thick flowable liquids, pastes, gels, etc.

Typical dyeing compositions of the various classes described above areset forth below:

(1) ALKALINE COMPOSITIONS General range Preferred range Any of the dyes,surface active agents, alkalies, thickening agents, acids andcombinations thereof set forth above may be used in the proportionsspecified in the table immediately above.

(2) ACID COMPOSITIONS The acid compositions are similar to the abovealkaline compositions, except that the alkali is omitted, and the acidis added to a pH of 2.57, preferred 3.56. The surfactant may be anionic,cationic or non-ionic or suitable mixtures of these, and any of thesementioned above may be used. The choice of thickener is somewhat morelimited, to alkylcellulosics, such as methylcellulose, and inorganics.In certain cases the surfactant, itself, acts as a thickener.

(3) OXIDATION DYE COMPOSITIONS The naphthoquinone imines utilized inthis invention are generally compatible with oxidation dyes.Accordingly, they can be used in oxidation dye compositions. Suitablecompositions contain 15% ammonia, 23% hydrogen peroxide or ureaperoxide; 0.005% to 2% oxidation dye components; 0.001% to 3%naphthoquinone imine as defined above, as well as surfactants,thickeners, etc. By way of illustration in this connection the followingoxidation dye components can be utilized in formulating thiscomposition: o-phenylenediamine, mphenylenediamine, p-phenylenediamine,p-toluenediamine, nitro-p-phenylenediamine, 4-nitro-o-phenylenediamine,p-aminodiphenylamine; 4,4-diaminodiphenylamine;4,6-dinitro-2-aminophenol; 4-nitro-2-aminophenol; 2,4-diaminoanisole,hydroquinone, resorcinol, p-aminophenol; 1,2,4-trihydroxybenzene;1,2,4-triacetoxybenzene.

The dyeing compositions of this invention can be prepared by theconventional methods used in the hair dyeing art. Thus, they can beprepared by dissolving or suspending the dye in water in the desiredconcentration. Water miscible organic solvents can be employed tofacilitate solution of the dye; in this event, the dye can be dissolvedfirst in the solvent and then diluted with water. The dispersion of thevarious ingredients can also be facilitated by heating the compositionat temperatures varying from 40 C. to 110 C., either before dilutionwith water or afterwards.

When the dye used in the compositions of this invention is naphthazarinintermediate, it may be employed in the crude state, directly asobtained from its preparative medium. The preparation of NI iswell-known and is accomplished by the reduction of1,5-dinitronaphthalene by means of S (sulfur dissolved in sulfuric acidor oleum). When the reaction mixture is poured on ice, and the aqueoussolution clarified and neutralized, NI is precipitated, and afterrecovery may be used without further purification in hair dyeingcompositions.

However, it is an aspect of this invention to provide a novelpurification method for NI, which then surprisingly enhances itsproperties in hair dyeing compositions. This purification methodconsists of heating NI with a. -20% aqueous solution of a secondary ortertiary alkanolamine, such as diethanolamine or triethanolamine or amorpholine, at about 100 C., for brief periods (10 minutes to one hour).The NI is then recovered by dilution with brine, filtration, and Washingwith brine. The alkanolamines which may be used, besides diethanolamineand triethanolamine, are such, for example, as: diisopropanolamine,triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine,diisopropylethanolamine, dimethylisopropanolamine,N-hydroxyethylmorpholine, and N-hydroxyethylpiperidine. Also suitableare 'morpholines, such as morpholine, N-methylmorpholine clearer andbrighter shades on hair, wool and nylon;

its dyeing compositions show greater storage stability. The priormethods of purifying NI show considerable deficiencies over the methodof this invention. Thus,

recrystallization from glacial acetic acid gives low recovery of NI, aswell as contamination with insoluble self-condensation products. Thepurification through the leuco compound leads to the reprecipitation ofmany of the impurities, and poor quality of the NI so obtained.

The following examples are further illustrative of the presentinvention. It is to be understood, however, that the invention is notlimited thereto.

In the example below reference is made to various dyeing procedures.These procedures are identified as follows PROCEDURE I Hair dyed from analkaline bath A mixture as follows was diluted with 50 ml. of water,

and the whole heated at 60 C. for one hour:

G. Dye 0.25 Ethanol ...a 0.35 Ethanolamine 4.0 Sodium N methyl Noleoyltaurate (Igepo T-33) Sodium carboxymethylcellulose 3.0

The mixture was then further diluted with water to a volume of cc., andcitric acid was added to give a pH of 9.9. The dye composition soobtained was poured on natural gray hair, permanent-waved hair, andbleached hair and allowed to remain for 20 minutes at 30 C. Afterwards,the hair was rinsed in clear water and dried in air.

PROCEDURE 1(a) In this procedure the same dyeing steps and mixtureutilized in Procedure I was employed. However, this mixture, before anydilution, was heated at C. for 10 minutes. Then 50 ml. of water wasadded, the mixture was heated at 60 C. for one hour, and the Volume wasadjusted to 1000 ml.

PROCEDURE II Hair dyed from an acid bath A mixture was prepared asfollows:

Dye 0.3

Ethanol z 0.35 Nonylphenoxypoly (ethyleneoxy) ethanol (Igepalco-730) 1.0

Methylcellulose 2.0

Water to 100 ml. Lactic acid to pH 3.5-ca. 0.25 g.

This composition was poured on normal gray, permanent-waved, andbleached hair and left in contact for 20 minutes at 30 C.

PROCEDURE III Hair dyed from peroxide bath The following composition wasprepared:

28% ammonia10.0 ml. Water to 100 ml.

A 30-ml. aliquot of this composition was mixed with 30 ml. of 6%hydrogen peroxide and the mixture poured on natural gray hair andallowed to remain there for 40 minutes at 30 C. The hair was then rinsedwith clear water, and shampooed.

13 I Example 1 Hair dyed with NI from alkaline baths.-Procedure I abovewas followed in which -amino-8-hydroxy-1,4- naphthoquinone-l-imine (NI)was used as the dye. All

hair was dyed a strong level reddish blue shade, fast. to 5 Hair dyedwith NI from an acid bath.Procedure II above was followed using5-amino-8-hydroxy-1,4-naphthoquinone-l-imine (NI) as the dye. When thiscomposition was poured on normal gray, permanent-waved and bleached hairand left in contact for 2-0' minutes at 30 C., as described in theprocedure, all was dyed a reddish blue shade, stable to rinsing,shampooing, and rubbing.

Example 3 Hair dyed with NI from peroxide bath.Procedure III above wasfollowed using 5-amino-8-hydroxy-1,4- naphthoquinone-l-imine (NI) as thedye. This dyed the hair a bright blue shade of excellent levelness, fastto rubbing.

Example 4 Purification of NI by treatment with alkanolamines. A sampleof naphthazarin intermediate was prepared by a known method as follows:

In 540 g. 100% sulfuric acid (monohydrate) was dissolved 2-0 g. sulfurpowder at 90-95 C. Then, at this temperature range, was added 40 g.1,5-dinitro-naphthalene portionwise over a period of one hour, and themixture heated for another hour. An additional 68 g. monohydrate wasadded, and the mixture was finally heated for one-half hour at 95 C. Thebatch was allowed to cool and to stand at room temperature for about 16hours. It was then poured onto 2000 g. ice, the solution clarified, andthe sulfur residue washed with 500 ml. Water. The combined filtrateswere neutralized with ammonia to a pH of 7, while 'keepingthetemperature below C. The precipitate of NI was filtered ioff, washedwith 1000 ml. water, pressed dry, and dried in air at 80 C. The crude NIthus obtained was used in the subsequent purification procedure asfollows:

A mixture composed of 40 g. of crude naphthazarin intermediate and 50 g.of diethanolamine in 300 g. of

water was heated at 100 C. for 30 minutes. The dye dissolved completely,and the solution on cooling was poured into 500 ml. of brine. At thispoint S-amino- 8-hydroxy-l,4-naphthoquinone-1-imine repricipitated andcomposition, prepared according to the method of 'Procedure I, andstored at 50 C. showed no loss in strength or change in shade when thedyeing was repeated after three months. In comparison the crude 'NI wasless soluble, gave duller shades on hair, and its dyeing compositionprepared according to Procedure I, on 'being stored for 3 months at 50C., and then re-applied to the hair showed a change in shade toward thebrighter, and a loss of 50% in dye strength.

When the above experiment was repeated using triethanolamine instead ofdiethanolamine, similar improvements in solubility, dyeability of hairand storage stabiliity were observed.

14 (A) CONDENSATION OF NI AND ALIPHATIC AMINES Example 5 Preparation ofN-propyl NI derivative.A mixture of 14 g. (0.075 mole) of5-amino-8-hydroxy-1,4-naphthoquinone-l-imine and 20 g. (0.34 mole)n-propylamine in 60 ml. water was heated at C. for 10 minutes. Thereaction mixture was diluted with 600 ml. of 10% brine, filtered aftercooling, and the cake was washed with 10% brine, and finally dried at C.The product has the structure indicated below according to theelementary analysis and infra-red spectrum. It is a black powder.

ll NH2 0 When applied to normal gray hair by the method of Procedure I,the alkyl derivative of this example gave a level grayish bluecoloration which was fast to shampooing and rubbing.

Example 6 Following the same synthesis procedure described in the firstparagraph of Example 5, utilizing the same molar proportions of N1 andalkylamine, but substituting n-butylamine for the propylamine, thecorresponding N-butyl compound is obtained which may be described as:

When applied to gray hair in accordance with Procedure I, it gave thehair a grayish blue color.

Example 7 Following the same synthesis procedure described in the firstparagraph of Example 5, utilizing the same molar proportions of NI andalkylamine, but substituting nhexylamine for the propylamine, theN-hexyl product is obtained, which may be described as:

Example 8 Preparation of N-hydroxyethylaminoethyl NI derivative.Amixture of 20 g. naphthazarin intermediate and 24 g.N-(Z-hydroxyethyl)ethylenediamine in 200 ml. water was heated 10 minutesat 85 C. After cooling, the reaction slurry was diluted with ml. 20%brine, and the dye was precipitated with 100 ml. 40% zinc chloridesolution. After filtering and washing with brine the dye was dried at 80C. The dye had the structure indicated below. It is a black powder whichdecomposes at 235C. and dyes natural gray and bleached hair in shades ofgray when applied by Procedure I.

Example 9 Preparation of N-substituted polyhydroxyalkyl NI derivative.Amixture of 14 g. naphthazarin intermediate and g.2-amino-2-methyl-1,3-propanediol in 150 ml. water was heated 10 minutesat 100 C. and poured into 200 ml. 20% brine. After 3 hours stirring, thedye was filtered off and washed with 20% brine until free of excessamine and dried. The dye had the structure indicated below. This is ablack powder that decomposed at 265 C. Nitrogen calculate, 9.87%; found,9.10%.

When the dye of this example was applied to normal gray hair by themethod and with the adjuvants of Procedure I, it gave a reddish blue huewhich was uniform and fast to washing and rubbing. When applied to grayor bleached hair with triethanolamine in place of ethanolamine as thealkalizing agent, it gave a clear blue shade of good rub and shampoofastness.

Example 10 A mixture of 40 g.5-an1ino-8-hydroxy-1,4-naphthoquinone-l-imine and 120 g.tris(hydroxymethyl)methylamine in 300 ml. water was heated at 80 C. Then200 ml. ethanol was added, and the dye dissolved completely. Thesolution was boiled for 4 hours under reflux conditions. After this timethe alcohol was distilled oif, and the slurry was diluted with 2000 ml.of brine (20% After cooling, the dye was filtered, washed with 5% brineand dried. Its structure is:

no lTIC(OH OH) I HzN Analysis.Calcd for C14H1'1N205Z N, 9.90%. Found:

When applied to gray hair in accordance with Procedure I, it dyes hairreddish blue in good strength. When triethanolamine is used in place ofthe ethanolamine of Procedure I, this composition dyes gray hair blue.

(B) CONDENSATION OF NI AND ALIPHATIC PO'LYAMINES Example 11 Preparationof trimethylene derivative of NI uct had the formula above. Nitrogencalculated, 13.4%; found, 12.9%.

16 When the product was applied to normal gray hair by the methods ofProcedures I and 1(a) above, it gave a strong bluish gray coloration,fast to shampooing and rubbing.

Example 12 Preparation of 3,3'-iminodipropyl derivative of NI A mixtureof 25 g. (0.136 mole) of 5-amino-8-hydroxy- 1,4-naphthoquinone-l-imineand 25 g. (0.191 mole) of 3,3-iminodipropylamine in ml. water was heatedfor 15 minutes at 100 C. After cooling, the product was precipitated bythe addition of 250 ml. of 20% brine, filtered off, washed with brine,and dried in air. It had the above designated structure. Nitrogencalculated, 14.8%; found, 15.1%.

When the dye was applied to hair by Procedure I, it showed a stronggreenish blue shade on natural gray, bleached and permanent-waved hair.When applied to hair by Procedure 1(a), the shade was bluish gray.

When these compositions containing the dye were stored at 50 C. for 3months and the dyeing on hair repeated, there was no diminution in dyestrength and no change in shade.

Following the same synthesis procedure described above in paragraph 1 ofExample 12 and utilizing the same molar proportions, unless otherwiseindicated, the polyamines and NI are reacted as indicated in column 3below. The compounds produced may be described by the formula:

wherein R'-- is a divalent radical as appears in column 2.

The dyeing results obtained with the products of this type are given inthe table below. The product used is A mixture of 188 g. (1 mole) NI and137 g. (1 mole) o-phenetidine were heated with stirring for 4 hours in1000 ml. 80% acetic acid with the addition of 140 g. sodium acetate(anhydrous). The color of the batch after 2 hours changed from reddishblue to greenish blue. After cooling the dye was filtered off and washedwith brine, then with a little water and dried. The product wasS-aminoS-hydroxy-l,4-naphthoquinone-1-(o-ethoxyphenyl)imine. It dyedgray and bleached hair in level blue shades when applied by Procedures Iand II.

Following the same synthesis procedure described in Example 17, unlessotherwise indicated, NI was reacted with the hydroxy or alkoxy aromaticamine as indicated in column 3 below. The compounds produced may bedescribed by the general formula:

l "NHz wherein R is a monovalent radical as appearsin colurnn 2.

Example i 2 No. Constitution R= Preparatlon 1s .NI plus p-phenetidinef19 NI plus o-anisidine.

NI plus p-anisidine.

NI plus p-amjnophenol; 4 hrs. boiling in glacial acetic acid.

NI plus o-aminophenol; 4

Q hours boiling in glacial acetic l acid. H

23 Q NI plus m-aminophenol.

The product'of Example 21 when used in Procedure I gave to gray hair ablue color. When triethanolamine was used in place of the ethanolaminein Procedure I, gray hair was also dyed a blue color.

The product of Example 23 gave gray hair a grayish blue'color whenapplied by Procedure I.

acetic acid. The batch was filtered warm to remove insol-ubles and thefiltrate was neutralized with ammonia 18 to a pH of 6.8 to 7.0. Theprecipitated dye was filtered off and dried. The product had thefollowing structure:

Hall; A

When applied to gray hair by Procedures I, II and III, it showed levelblue coloration. The same procedure withN,N-bishydroxyethyl-p-phenylenediamine gave a dye with similarproperties on hair.

(D-l) CONDENSATION OF NI WI'UH DIALKYL- AMINO AROMATIC AMINES Example24A N CH3 2 HaN g A solution of 4.2 g. (0.031 mole)N,N-dimethyl-pphenylenediamine in 75 cc. glacial acetic aid was added to5.7 g. (0.03 mole) naphthazarin intermediate in 100 cc. glacial aceticacid at reflux. The mixture was heated at reflux for one hour, filteredand the filtrate poured into 500 cc. 20% brine. The pH was adjusted toneutral 'by means of ammonia in order to precipitate the dye. Theprecipitate was filtered olf, redissolved in boiling dioxane. Thesolution was clarified and added to 20% brine. The precipitated dye waswashed with water and dried. The product d'yed hair greenish blue byProcedure I, and somewhat bluer in shade by Procedure II and had thestructure shown above.

(D-2) CONDENSATION OF NI WITH 1 NITROANILINES Example 24B A solution of4.8 g. (0.031 mole) nitro-p-phenylenediamine in 50 cc. glacial aceticacid was added dropwise to a refluxing solution of 5.7 g. (0.03 mole)naphthazarin intermediate in cc. glacial acetic acid and refluxing wascontinued for one hour. The hot mixture was filtered and the filtratepoured into 600 cc. 20% brine and the precipitated product was filteredoff. The dried precipitate was heated in 75 cc. dioxane at reflux, thehot mixture filtered, and the filtrate added to 500 cc. 20% brine. Theprecipitated material was filtered off, washed with water and dried. Theproduct 19 was a dark blue powder havin g'the above designatedstructure. 'It' dyed hair greenish blue-"when applied by Procedure I.

When in the above example, the nitro-p-phenylenediamine was replaced bya molecular equivalent of 4-amino-2-nitro-phenol, there was obtained asproduct 5-amino-8-hydroxy-l, 4 naphtho quinone-l-(4-hydroxy-3-nitrophenyl)-amine, which had" a "similar shade and affinity on hair.

Example 24C Ho N M at. ll

A solution of 6.3 g. (0.045 mole) m-nitro-aniline in 90 cc. glacialacetic acid was added dropwise to refluxing solution of 5.7 g. (0.03mole) naphthazarin intermediate in 90 cc. glacial" acetic acid and themixture refluxed for one hour. The mixture was filtered hot and thefiltrate poured into 600 cc. brine whereupon the precipitated materialwas filtered off. The dried precipitate was reprecipitated from hotdioxane solution by the addition of 20% brine. The dye was filtered off,washed salt-free with water and dried. The product had the structuredesignated above and dyed hair greenish blue when applied by ProcedureI.

(E) CONDENSATION OF NI WITH HETEROE I CYCLIC AMINES Example 25 shade ofblue.

ll N/ V Example 26 i ll HzN O A mixture of 5.7 g. (0.03 mole) NI and 3.4g. (0.031 mole) 2,6-diaminopyridine was heated at reflux in ml. glacialacetic acid for 4 hours. After cooling, the solution was diluted with;300 ml.- 20% brine and the precipitated product was filteredoif. The dyewas washed W 5 a t fi Wit 2 rin t en s e sa free with water and dried.The product had the structure designated above. Hair was dyed greenishblue by this .productapplied byrlrocedureslr.and-.II. U Example- 27 Hm s2 I I A mixture of 5.7 .g. (0.03 mole) NI and 5.0 (0.0302 mole)5-amino-Z-marcaptobenzimidazole was heated in 100 ml. acetic acid for 4hours at C. The .batch was filtered hot and the filter-cake washed withisopropanol and dried. Theproduct, which has the structure drawn above,dyed hair a green shade blue, fast to rubbing and shampooing, whenapplied by Procedures I andII. Y Y t v A mixture of 5.7 g. (0.03 mole)NI, 6.4 g. (0.032 mole) 2-amino-naphthol[1,2]thiaz0leand 10 g. anhydroussodium acetate in 250 ml. 80% acetic acid was heated for 4 hours at 90C. The batch was filtered from insoluble impurities at 70 C., and thefiltrate neutralized with amrnonia while-coolingto-pH'H).The-'precipitate'was fil-' tered off, washed-with water andv dried. Theproduct had the structure indicated above. 'It dyed hair by'Procedures Iand II in greenish blue shades of good shampoo fastness.

"('F') 'CONDENSATIONOF'NI W-ITHAMINO- i BENZYL ALCOHOLS Example 29 HzCH21 22 wherein R is the monovalent radical as appears in colfor 3 monthsgave similar dyeings on hair with no change umn Zbelow. in shade andstrength compared to the initial dyeings.

Example I Example 35 Cmstlmtmn PIP/Farah 5 Dyeing hair with alkyl andaryl derivatives of NI from so NI plus o-aminobenzyl alcohol. cid bathHtl) N-R CHZOH 31 I CH2OH NI plus p-aminobenzyl alcohol. 10

' II (G) CONDENSATION OF NAPHTHAZARI HZN WITH AMINES Example 32 5Procedure II above is followed using a series of derivatives of thegeneral structure above, in which R has the In 30 ml. water, 4 g. (0.02mole) sublimed naph- 1 h in 1 mn1b l w, thazarin and g. (0.09 mole)diethylenetriamine were h results are as foll heated at the boil forfive minutes. The solution was poured into 50 ml. brine and the productprecipi- 20 tated with 50 ml. of 40% zinc chloride solution. The Coloron gray Color on bleached precipitate was filtered off, washed withbrine, then with R a little water and dried. The precipitation of thedye can CHeCH2NHC2H4OH Gray Gray.

also be performed by means of sodium chloride, potas- C(CH2OH)3 m siumchloride or sodium sulfate in place of the zinc Grayish blL I QIII:Grayish blue. chloride, but the yield is lower. The product dyed naturalp Hydmxyphenyl g:

gray and bleached hair a strong gray color when applled by Procedures Iand II. The product may be described by the following formula: Example36 I ll The dye prepared by the reaction of diethylenetriamine with twomolar equivalents of 5-amino-8-hydroxy-1,4-

naphthoquinone-l-imine was incorporated into an acidic hair dyeingcomposition of Procedure II and dyed on A hair. There was obtained aslate blue coloration of normal gray hair, permanent-waved hair andbleached hair, fast to shampooing and rubbing.

Similarly, the dyes prepared using other diamines in place ofdiethylenetriamine, showed the following dyeings:

Example 33 The procedure of Example 32 was followed, except that inplace of the diethylenetriamine, 3,3'-iminodipropylamine was employed.The product obtained can be Diamine: Color on gray hair described by thefollowmg formula Triethylenetetramine Grayish blue. HON-CH2-CH2-CH2-NHCH2CH2-CH2NH2 Tetraethylenepentarnine Slate gray.

l 1,3-diaminopropane Bluish gray.

EXAMPLES OF OTHER DYE BATH COMPOSITIONS v t v Example 37 H O A mixturewas prepared of the following components When applied to natural grayand bleached hair by y Stirring them together thoroughly at about CJProcedures I and II, it gave very strong bluish gray colors. G.

Example 34 The dye, S-amino-S-hydroxy-1,4-naphthoquinone-1- Sulfonatednaphthazarin intermediate.A solution of i gg f xg z ggg 1111' 150p topanol) u 5.65 g. 5-amino-8-hydroxy-1,4-naphthoquinone-1-iminepolyoxyethylated igfigggf in 58 oleum was P p y gradually Sodiumcarboxymethyl cellulose Z0 adding the naphthoquinone imine powder to theoleurn Water to make 50 m1 while keeping the temperature at about 25-30C. The solution was then heated at 100.110 C. for 2 hours, or 60 whenthe mixture Was homogeneous, it Was cooled to until a test sample wascompletely soluble in water. The room temperature, diluted to 100 ahdthe P adjusted mixture was poured onto 200 g. ice and 40 g. sodium to yaddition of Citric aoidchloride added. The'precipitated5-amino-8-hydroxy-l,4- The composition so p p was poured on naturalnaphthoquinone-l-imine monosulfonic acid sodium salt y hair, on bleachedhair, and on Permanent-waved was recovered by filtration, washing with20% brine, then and alloWed to remain n Contact With the hair for with aminimum of cold water to remove salt, and drying 2025 minutes at aboutAttol'wards, the hair Was at 80 C. in air. removed, shampooed and dried.The various kinds of The product was applied t normed gray h i d hairwere all dyed a level greenish blue of fairly similar bleached hair byProcedure I giving a moderately strong fast to fllbhlhg and ShamPooihg-When-the above reddish blue dyeing. When triethanolamine was substituteddescrlbed mp l l n w s st red at 50 C. for 3 months for ethanolamine inProcedure -I, the dyeings were someand another dyeing on hair Performed,there Was loss what greener blues, When applied by P d r 11, h ofstrength or shade change compared with the original dyeings weregreenish blue. In allcases the dyeings were dyeing.

level, and uniform as between gray and bleached hair, In the abovecomposition, in place of the dye S-aminoand fast to rubbing. Thecompositions stored at 50 C. 8-hydroxy-1,4-naphthoquinone-l-imine theremay be sub- 23 stituted an equal weight of any of the following dyes,with the dyeing results as indicated below: -amino-8-hydroxy-1,4naphthoquinone-1-n-butyliminebluish gray of uniform shade on the variouskinds of hair Product of Example 9-blue; uniform on the various kinds ofhair Product of Example 13grayish blue; uniform on the various kinds ofhair Example 38 The following composition was'prepared' by mixing theingredients at about 50 C.

G. The dye, N ,N '-trirnethy1ene-bis-S-amino 8hydroxy-l,4-naphthoquinone-l-imine (product of Example 11) (wet with 0.5ml. ethanol) 0.15 Diethylenetriamine g 3.0 Sodium N-coconut acidN-methyl taurate 3.0 Methylcellulose 3.0

Water to make 50 ml.

When the mixture was homogeneous, it was cooled, the volume adjusted to100 ml. by the addition of water, and the 'pH adjusted to 9.0 by theaddition of acetic acid. It was then poured on gray hair, bleached hair,and permanent-waved hair, where it was allowed to remain for 30 minutesat 30 C. The hair was shampooed and dried. The various kinds of hairwere all dyed a strong level shade of grayish blue, fast to shampooingand rubbing.

In the above composition, in place of the above-named dye, there may besubstituted an equal weight of the following dyes, with the dyeingresults as indicated:

Product of Example l0--strong blue shade on various kinds of hair;composition stable on storage for 3 months at 50 C.

N -p-acetamidophenyl-S-amino 8 hydroxy 1,4 naphthoquinone-1-imineblue onthe various kinds of hair N -benzyl 5 amino 8hydroxy-1,4-naphthoquinone- 1-iminegreenish blue on the various kinds ofhair G. The dye, N ,N (3,3'-iminodipropyl)bis-S-amino-S-hydroxy-1,4-naphthoquinone 1 imine (product of Example 12) (wet with0.5 ml. isopropanol 0.15 N-phenyldiethanolamine 3.0 Lauriediethanolamide 3.0 Sodium alginate 1.0

Water to make ml.

After cooling, the volume was adjusted to 100 ml., and the pH to 9.5 byaddition of tartaric acid. This mixture was poured on natural gray,waved, and bleached hair where it was allowed to remain for 30 minutesat 30 C., whereupon. the hair was removed, shampooed, anddried. Thevarious kinds of hair were all dyed a greenish blue shade of goodstrength which wasfast to shampooing and rubbing. When the abovecomposition was stored at 50 C. for 3 months, and the dyeing repeated,there was essentially no difference, either in shade or strength fromthe initial dyeings.. W

In the above composition, in place of the dye therein mentioned, theremay be substituted an equal weight of any'of the following dyesywith the'dyeing'resultsas indicated:

Product of Example 15bluish gray shades on all kinds of hairS-amino-S-hydroxy 1,4 naphthoquinone 1 cyclohexylimine-bluish gray ofmoderate strength N (p-carbamoy1phenyl) 5 amino 8 hydroxy 1,4

naphthoquinone-1-iminegreenish blue on all kinds of hair In the abovecomposition, in place of the phenyldiethanolamine, there may besubstituted an equal weight of diethanolamine, N-methyldiethanolamine,or dimethylisopropanolamine with essentially the same results in thedyeings.

In the above composition, in place of the lauric diethanolamide, theremay be substituted an equal weight of myristic diethanolamide,polyoxyethylated fatty alcohol or lauric isopropanolamidewithessentially the same dyeing results.

Example 40 The following composition was prepared: v The dye,

G. 0.1 H(|) lfil-C2H4NHC2H NH2 Ethyleneglycol monostearate 2.0Polyacrylic acid 1.0 Water to make 50 ml. Citric acid to pH 4.

This mixture was poured on natural gray, permanentwaved, and bleachedhair, and allowed to remain in contact with the hair for 30 minutes at30 C. Afterwards, thehair was shampooed and dried. All specimens of hairwere dyed a strong shade of gray, level, and uniform as among thevarious types of hair, and fast to shampooing and rubbing. When thecomposition was stored for 3 months at 50 C. and the dyeing repeated,there was no change in shade or strength compared with the originaldyeings.

In the above composition in place of the dye mentioned, there may besubstituted the following dyes, with dyeing results as indicated:

N (p-hydroxyphenyl)-5-amino 8 hydroxy-1,4-naphthoquinone-l-imineblue onthe various types of hair N -tris(hydroxymethyl)methy1 5 amino 8hydroxy- 1,4-naphthoquinone-l-imine-strong blue on the varimonostearate,there may be substituted an equal weight of oleic ethanolamide, a fattyalcohol polyglycol ether,

cetyl pyridinium bromide, or dodecylbenzyl trimethyl ammonium chloride,with essentially the same dyeing results.

In the above composition the polyacrylic acid may be omitted, giving amuch less viscous mixture which is otherwise similar in dyeingproperties.

This composition was allowed to remain in contact with normal gray,permanent-waved, and bleached hair for 20 minutes at 32 C., and the hairwas then removed and shampooed. All these types of hair were dyed asimilar shade of level blue of high strength, which was fast tos'hampooing the rubbing. The composition was stored at 50 C. for 3months, then gave. dyeings similar in strength and shade to the originaldyeings.

Example 42 A mixture was prepared of the following components:

The dye, product of Example ..i 0.060 p-Phenylenediamine 0.060

m-Aminophenol Nitro-p-phenylenediamine 4-nitro-o-phenylenediamineResorcinol I 0.100 Isopropanol j 2.5 Sodium lauryl sulfate 1.00Propylene glycol 10.00 Polyethoxylated octylphenol 15.00 Ammonia 28%10.0ml. i Water to make-100 ml.

To 30 ml. of this composition wasadded 30 ml. 6% hydrogen peroxide, andthis mixture was poured at once on natural gray hair where it wasallowed to remain for 45 minutes at 30 C. The hair was then rinsed andshampooed. The hair was dyed a light brown shade which was level andfast to rubbing andshampooing.

Although the invention has been described with refer: ence to specificforms thereof, it will be understood that many changes and modifications'may be made without departing from the spirit of this invention. 1

What is claimed is: I

1. A method for dyeing living human hair on the head which comprisesimpregnating said hair with a tinctorial amount of a hair substantivenaphthoquinnne imine selected from the group consisting of:

and tautomeric forms thereof wherein: I

(1) X is selected from the group consisting of the monovalent radical-'R and the divalent radical R', wherein R may behydrogen, alkyl having1 to 6 carbon atoms, hydroxyalkyl having 2 to 6 carbon atoms in thealkyl chain and up to 3 hydroxy groups, -(alkylene-NH), -alkylene-OHwherein n is a number from 1 to 3 and alkylene has up to 4 carbon atoms,-(alkylene-NH) -alkylene-N-H wherein n is a number from 1 to 3 andalkylene has up to 4 carbon atoms, monovalent cycloalkyl having up to 6carbon 26: atoms in the ring, said cycloalkyl may be substituted with agroup selected from the class consisting of hydroxy, oxo, methyl, chloroand methoxy monovalent aryl, monovalent aralkyl and monovalentheterocyclic radicals; and wherein R- may be divalent alkylene having 3to 6 carbon atoms, divalent hydroxyalkylene radicals containing from 3to 6 carbon atoms and up to 2 hydroxy groups, -(alkylene-NH) -alkyleneinwhich n is from 1 to 3 and the alkylene moiety has from 1 to 6 carbonatoms, divalent cycloalkyl having up to six carbon atoms in the ringdivalent arylene, divalent aralkyl and divalent hetezrocyclic radicals;(2) v is a whole number from 1 to 2: r being 1 when X is monovalent, andr being 2. when X is divalent; and (3) A, B, C, D, E and G are selectedfrom the group consisting of hydrogen, chlorine, bromine, sulfo, alkyland the radical --HNR in which R has the value described to it above andwherein the radicals selected from the group consisting of A and B mayalso be hydroxy; said aryl and aralkyl radicals being monocyclic orbicyclic having up to 12 carbon atoms in the respective ring systems andsaid heterocyclic radical being selected from the group consisting of2-pyridyl,

3 pyridyl, 4 pyridyl, 6-amino 2 pyridyl, 2-

methyl-4-thiazolyl, 4-quinolyl, S-quinolyl, 7-quinolyl,

Z-imidazolyl, S-benzimidazolyl, 2-benzothiazoly1,2-mercapto-S-benzthiazolyl and 2-naphtho[l,2] thiazolyl.

2. A method according to claim 1 wherein the naphthoquinone imine isnaphthazarin intermediate.

3. A method according to claim 1 wherein said naphthoquinone imine is5-amino-8-hydroxy-1, 4-naphthoquinonel-imine or tautomers thereof.

4. A method according to claim 1 wherein said tinct'orial amount is inthe range of from about .01 to 5% by weight.

5. A method according to claim 1 wherein naphthoquinone imine is of thegroup:

and tautomeric forms thereof in which n is a whole number from 1 to 3said alkylene radical having up to 4 carbon atoms.

6. A method according to claim 12 wherein the radical H (alky1ene-N) His selected from the group consisting of -CH CH -NH--CH -CH NH and 7. Amethod according to claim 1 wherein the naphthoquinone imine is of thegroup:

chain contains from 2 to 6- carbon atoms and from 1 to 3 hydroxy groups.

27 8. A method according to claim 7 wherein R'is selected from the groupconsisting of CHzOH ornoH C-GHzOH and -co or-norr onion 9. A methodaccording to claim 1 wherein the naphthoquinone imine is of the groupconsistingof:.

1 r 9 (1W0 ill-1X1) 11H.

and tautomeric forms thereof wherein R' is a divalent radical selectedfrom the group consisting of alkylene and the radical (alkylene-NH)-alkylene-, wherein n is a whole number from 1 to 3.

10. A method according to claim 9 wherein -R'- is selected from thegroup consisting of (1H Q /R1 A N Q 1 Ila-NH O and tautomeric formsthereof wherein R and R are selected from the group consisting of H, andhydroxyalkyl having up to 3 carbon atoms and 2 hyd roxy groups, at mostone of R and R being hydrogen; and R is selected from the groupconsisting of H and the radical in which R and R have the same valuesascribed to them above. 7 v

12. An aqueous hair dyeing composition containing from .01 to by weightof a hair substantive naphthoquinone imine dye and from 0.1% to about10% by weight of the composition of an alkalizing agent to impartthereto an alkaline pH, said dye being selected from the groupconsisting of:

i l X G H:c E D and tautomeric forms thereof wherein: (1) X is selectedfrom the group consisting of the monomonovalent aralkyl and monovalentheterocyclic radi 28 valent "radical R and'the divalent "radical.,-R''-, 'wherein -'-K may be hydrogen, monovalent-cycloalkyl having upto"6 carbon'atoms in the ring, said cycloalkylmay be substituted with agroup selected from the class consisting ofhydroxy, 0x0, methyl, chloroand methoxy, alkyl having 1 to 6 carbon atoms, hydroxyalkyl having 2 to6 carbon atoms in the alkyl chain and up to 3 hydroXy groups,{alkylene-NH alkylene- OH whereinn is anumber from 1 to 3 and alkylenehas up'to'4 carbon atoms, {alkylene-NHL?- a-lkylene-NH- wherein n 'is anumber from 1 to 3 and alkylene'has'up'to'4 carbon atoms, monovalentaryl,

cals and wherein R' may be divalent alkylene'having 3 to 6 carbon atoms,divalent hydrox-yalkylene radicals containing from 3 to 6 carbon atomsand up to YZ-hydroxy; groups, (alkylene-NH) 3-alkylene-. in which n isfrom 1 to 3 and the alkylene moiety has from 1* to, 6 carbon atoms,divalentcycloalkyl having up 'to six carbon atoms in'the ring, divalentarylene, divalent aralkyl and divalent heterocyclic radicals; (2), r isanumber froml to 2, r being 1 when X is, monovalent, and r is 2 when X isdivalent; and (3) A, B, C, D, E and G are selected from the groupconsisting of hydrogen, chlorine, bromine, sulfo, alkyl and the radical-NHR' in which-R has the value ascribed to it above and wherein radicalsselected from .the group consisting of A and B may also be hydroxy; saidaryl and aralkyl radicals being .monocyclic or bicyclic having up to 12carbon atoms in the respec- ,tive ring systems and said heterocyclicradical being selected from the group consisting of. 2-pyridyl, .3- Ipyridyl, '4 pyridyl, 6-amino-2-pyridyl, 2-rnethyl-4- thiazolyl,4-quinolyl, '5-quinolyl, 7-quinolyl,' 2-irnidazolyl, S-benzimidazolyl,2-benzothiazolyl, 2-m'ercapto.

S-benzthiaiolyl and 2-naphtho[1,2] thiazolyl.-

. 13,. A hair dyeing composition according toclaim 12 wherein the pHisin the range of about 7.5 to 10.

14. A hair dyeing composition according to claim 12 wherein thealkalizing agent is an organic amine 15. A hair dyeing compositionaccording to claim 12 wherein the alkalizing agent is selected from thegroup consisting of monoalkanolamines, dialkanolamines andtrialkanolamines. 7

16; A composition according to claim 15 wherein the dye isS-amino-S-hydroxy-l,4-naphthoquinone l-imineor tautomers thereof.

References Cited UNITED STATES PATENTS ALBERT T. MEYERS, PrimaryExaminer D. R. ORE, Assistant Examiner Us. 01. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,516,778 June 23, 1970 Walter H. Brunner It is certified that errorappears in the above identified d that said Letters Patent are herebycorrected as patent an shown below:

Column 9, line 17 "primary" should read preliminary Column 26, line 3,after "methoXy" insert a semicolon; lines 17 and 18, "described" shouldread ascribed line 50, "claim 12" should read claim 5 Claim 10, insert asemicolon at the end of lines 3, 4, 5 and 7 respectively of this claim.

Signed and sealed this 19th day of January 1971.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Ir.

Commissioner of Patents Attesting Officer

